Unique and efficient adsorbents for highly selective and reverse adsorption and separation of dyes via the introduction of SO3H functional groups into a metal–organic framework

Abstract

In this study, an unsaturated Cu-based MOF, HKUST (Cu₃(BTC)₂), was fabricated and modified with sulfonate groups in two steps, leading to the construction of a novel sulfo-functionalized MOF. The prepared framework was utilized in the adsorption and separation of various organic dyes (MB, Er, FS, and MV). The adsorption process represented intriguing features due to the introduction of the SO₃H functional groups into the framework. Such an attractive feature has rarely been depicted in previous works. In addition to the substantially increased adsorption capacity of the modified framework compared with that of pristine MOF, a reverse and selective phenomenon was perceived in the cases of FS and MV. The sulfo-functionalized MOF could adsorb MV with high adsorption capacity but barely adsorbed FS, and the opposite condition was observed for pristine MOF. In addition, the prepared framework showed high selectivity in a mixed solution of dyes. On the other hand, the modified framework had no role in the first step of the adsorption and separation process and showed the same behavior as pristine MOF. Furthermore, the sulfonate functional groups could not be directly incorporated into HKUST. The experimental data followed the pseudo-second-order kinetics and the Langmuir isotherm model. Thermodynamic studies demonstrated an exothermic spontaneous mechanism for the dye adsorption process. The prepared adsorbents were capable of being recycled for four sequential cycles. Hereupon, this study presents a notably efficacious approach for the reverse performance of frameworks for the dye adsorption and separation process.